Rosin modified succinamic acid

ABSTRACT

The present invention relates to rosin modified succinamic acid which is useful in lowering the rebound values of rubber and increases the traction of tires containing said compound in the tread. The rosin modified succinamic acids are prepared by reacting abietylamine and/or dehydroabietylamine with succinic anhydride.

BACKGROUND OF THE INVENTION

Both natural and synthetic elastomers usually require the use of processing aids to assist mechanical breakdown and compounding. Materials such as mixtures of oil soluble sulfonic acids of high molecular weight with a high boiling alcohol, paraffin oils, blends of sulfonated petroleum products and selected mineral oils are conventionally used as processing aids. Additional examples include petroleum, paraffinic and vegetable oils, coal tar, petroleum residues or pitches and naturally occurring or synthetic resins.

One advantage in using processing aids is they assist the incorporation of fillers and other ingredients with low power consumption since they reduce internal friction in calendering and extrusion. By reducing the amount of friction during compounding, the temperature of the rubber will remain lower and thus minimize the possibility of scorch.

Various types of rosin acids have been used as extenders for high molecular weight SBR. See Properties of GR-S Extended With Rosin Type Acids, L. H. Howland, J. A. Reynolds, and R. L. Provost, Industrial and Engineering Chemistry, Vol. 45, No. 5, May 1953. Whereas reasonably good cured physical properties can be obtained with the rosin type acids, there are problems associated with their use which include cure retardation, high tack and poor low temperature performance, which limit their use as an extender in rubber formulations.

U.S. Pat. No. 4,478,993 discloses the use of decarboxylated rosin acid also known as thermal oil as a total or partial replacement for oil in a rubber formulation. Compared with the use of aromatic extending oils in rubbers, decarboxylated rosin acids provide comparable processing and low temperature performance and superior abrasive resistance.

U.S. Pat. No. 5,134,184 relates to rosin monomaleimides which are useful as a total or partial replacement for extender or processing oil in rubber formulations. The rosin monomaleimides are prepared by reacting abietylamine and/or dehydroabietylamide with maleic anhydride.

SUMMARY OF THE INVENTION

The present invention relates to rosin modified succinamic acid of the formula:

or mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

There is also disclosed a process for preparing rubber compositions which comprises a mixing a rubber selected from the group consisting of natural rubber, homopolymers of conjugated diolefins, copolymers of conjugated diolefins and ethylenically unsaturated monomers or mixtures thereof with a rosin modified succinamic acid.

There is also disclosed a rubber composition which comprises (1) a rubber selected from the group consisting of natural rubber, homopolymers of conjugated diolefins, copolymers of conjugated diolefins and ethylenically unsaturated monomers or mixtures thereof and a rosin modified succinamic acid of the formula:

or mixtures thereof.

The rosin modified succinamic acid is prepared by reacting abietylamine or dehydroabietylamine with succinic anhydride. The abietylamine and dehydroabietylamine are derived from rosin. Rosin is a solid resinous material that occurs naturally in pine trees. The three major sources of rosin are gum rosin, wood rosin and tall oil rosin. Gum rosin is from the oleoresin extrudate of the living pine tree. Wood rosin is from the oleoresin contained in the aged stumps. Tall oil rosin is from the waste liquor recovered as a by-product in the Kraft paper industry.

The aged virgin pine stump is the source of wood rosin. The stump is allowed to remain in the ground for about ten years so that its bark and sapwood may decay and slough off to leave the heartwood rich in resin. It is known that production of pine stump rosin can be artificially stimulated by injecting the herbicide, Paraquat, into the lower portion of the tree. This treatment of the stump produces Pinex™ rosin.

Rosins derived from both oleoresin and aged stump wood are composed of approximately 90% resin acids and 10% nonacidic components. Chemical treatment of rosins, such as hydrogenation, dehydrogenation, or polymerization are known which produce modified resins.

Succinic anhydride is reacted with abietylarnine or dehydroabietylamine under suitable conditions to form a compound having a rosin moiety connected to a succinamic acid. Dehydroabietylamine in a 90% purity is commercially available from Aldrich Chemical Company. Abietylarnine and dehydroabietylamine can be used individually or more commonly in mixtures with various amounts of other rosin amines including levopimarylamine, neoabietylamine, palustrylarmine, tetrahydroabietylarnine, pimarylamine, isopimarylamine, Δ-isopimarylamine, elliotinoylamine and sandaracopimarylamine. Therefore, in connection with the above formula, the rosin modified succinamic acid may also be derived from use of the above amines which are commonly found in admixture with abietylamine and/or dehydroabietylamine.

The succinic acid anhydride may be reacted with the abietylamine and/or dehydroabietylamine in a variety of mole ratios. Generally the mole ratio of succinic anhydride to abietylamine and/or dehydroabietylamine ranges from about 1.5:1 to about 0.75:1 with a range of from about 1.1:1 to about 0.9:1 being preferred.

An organic solvent may be used to dissolve the abietylamine or dehydroabietylamine. The solvent is preferably inert to the reaction between the succinic anhydride and the abietylamine and/or dehydroabietylamine. Illustrative of solvents suitable for use in the practice of this invention include: saturated and aromatic hydrocarbons, e.g., hexane, octane, dodecane, naphtha, decalin, tetrahydronaphthalene, kerosene, mineral oil, cyclohexane, cycloheptane, alkyl cycloalkane, benzene, toluene, xylene, alkyl-naphthalene, and the like; ethers such as tetrahydrofuran, tetrahydropyran, diethylether, 1,2-dimethoxybenzene, 1,2-diethoxybenzene, the monoand dialkylethers of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, oxyethyleneoxypropylene glycol, and the like; fluorinated hydrocarbons that are inert under the reaction conditions such as perfluoroethane, monofluorobenzene, and the like. Another class of solvents are sulfones such as dimethylsulfone, diethylsulfone, diphenolsulfone, sulfolane, and the like. Mixtures of the aforementioned solvents may be employed so long as they are compatible with each other under the conditions of the reaction and will adequately dissolve the abietylamine or dehydroabietylamine and not interfere with the reaction.

The reaction between the succinic anhydride and abietylamine and/or the dehydroabietylamine may be conducted in the absence or presence of a catalyst. Examples of catalysts that may be used include acid catalysts such as sulfuric acid, hydrochloric acid and toluenesulfonic acid. The amount of catalyst that may be used will vary depending on the particular catalyst that is selected. For example, when an acid catalyst is used, from about 5% to about 10% by weight of the abietylamine and/or dehydroabietylamine is recommended. However, it is preferred that no catalyst is used to avoid the formation of undesirable side products.

The reaction between the succinic anhydride and abietylamine and/or dehydroabietylamine may be conducted over wide temperatures. The temperatures may range from moderate to an elevated temperature. In general, the reaction may be conducted at a temperature of between about 0° C. to about 250° C. The preferred temperature range is from about 24° C. to about 150° C., while the most preferred temperature range is from about 56° C. to about 60° C.

The reaction may be conducted under a variety of pressures. Pressures ranging from about 0 psig to about 100 psig may be used to conduct the reaction.

The reaction is conducted for a period of time sufficient to produce the desired rosin modified succinamic acid. In general, the reaction time can vary from minutes to several hours. If the more sluggish reaction conditions are selected, then the reaction time will have to be extended until the desired product is produced. It is appreciated that the residence time of the reactants will be influenced by the reaction temperature, concentration and choice of catalyst, total gas pressure, partial pressure exerted by its components, concentration and choice of solvent, and other factors.

The process for the preparation of the rosin modified succinamic acid may be carried out in a batch, semi-continuous or continuous manner. The reaction may be conducted in a single reaction zone or in a plurality of reaction zones, in series or in parallel. The reaction may be conducted intermittently or continuously in an elongated tubular zone or in a series of such zones. The material of construction of the equipment should be such as to be inert during the reaction. The equipment should also be able to withstand the reaction temperatures and pressures. The reaction zone can be fitted with internal and/or external heat exchangers to control temperature fluctuations. Preferably, an agitation means is available to ensure the uniform reaction. Mixing induced by vibration, shaker, stirrer, rotating, oscillation, etc. are all illustrative of the types of agitation means which are contemplated for use in preparing the composition of the present invention. Such agitation means are available and well known to those skilled in the art.

Addition of the rosin modified succinamic acid to sulfur vulcanizable elastomers surprisingly lowers the rebound values and increases the traction of tires containing the compound in the tread. The term “rubber” or “elastomer” as used herein embraces both natural rubber and all its various raw and reclaim forms as well as various synthetic rubbers. Representative synthetic elastomers are the homopolymerization products of butadiene and its homologues and derivatives, as for example, methylbutadiene, dimethylbutadiene, chloroprene (neoprene synthetic rubber) and pentadiene as well as copolymers such as those formed from butadiene or its homologues or derivatives with other unsaturated organic compounds. Among the latter are acetylenes, e.g., vinyl acetylene; olefins, for example, isobutylene, which copolymerizes with isoprene to form butyl rubber; vinyl compounds, for example vinylchloride, acrylic acid, acrylonitrile (which polymerizes with butadiene to form NBR), methacrylic acid and styrene, the latter compound polymerizing with butadiene to form SBR, as well as vinyl esters and various unsaturated aldehydes, ketones and ethers, e.g., acrolein, methyl isopropenyl ketone and vinylethyl ether. Also included are the various synthetic rubbers prepared by the homopolymerization of isoprene and the copolymerization of isoprene with other diolefins and various unsaturated organic compounds. Additionally, included are the synthetic rubbers such as 1,4-cis polybutadiene and 1,4-cis polyisoprene and similar synthetic rubbers such as EPDM. The preferred rubbers for use with the rosin modified succinamic acid are natural rubber, polybutadiene, SBR and polyisoprene.

The rubber vulcanizates containing the rosin modified succinamic acid may be used in the preparation of tires, motor mounts, rubber bushings, power transmission belts, printing rolls, hoses, rubber shoe heels and soles, rubber floor tiles, caster wheels, elastomer seals and gaskets, wringers, hard rubber battery cases, automobile floor mats, mud flaps for trucks, ball mill liners, and the like. The preferred vulcanizate is a tire wherein at least one component thereof contains a rubber compounded with the rosin modified succinamic acid. Specific examples of components in the tire include the tread cap, tread base, sidewall, sidewall insert, innerliner, chafer, apex and wirecoat.

The rosin modified succinamic acid may be used in a wide variety of proportions in the rubber and may be a substitute, in whole or part for conventional extender or process oils. By the term “extender or process oils”, it is meant oils such as aromatic oils, naphthenic oils, paraffinic oils and the like as well as blends thereof. Specific examples of such oils include those largely composed of naphthenic and alkylated naphthenic hydrocarbons and mixtures thereof with various aromatic hydrocarbons. Such oils may be obtained from the high boiling fractions of the so-called naphthenic or mixed crude oils. They may comprise distillate fractions boiling above about 200° C. Suitable fractions are those at least 90 percent of which boil above about 250° C. as more volatile members may be lost during or after compounding and curing the rubber. Generally, the level of rosin modified succinamic acid that may be added to the rubber composition may range from about 1 phr (parts per hundred rubber) to about 50 phr. Preferably the amount of rosin modified succinamic acid is added ranges from about 2 phr to about 35 phr.

The following examples are presented in order to illustrate but not limit the present invention.

EXAMPLE 1 Preparation of N-(Abietyl) Succinamic Acid

A 2 liter round bottom flask was charged with 50 g (0.50 mole) of succinic anhydride dissolved in 300 ml of reagent acetone. The flask was flushed with nitrogen and the contents stirred. A dropping funnel containing 143 g (0.50 mole) of abietylamine dissolved in 300 ml of reagent acetone was attached and added over a period of 5 minutes, wherein an exotherm raised the reaction temperature to about 42° C. The resulting acetone solution was refluxed for an additional 1 hour. The amber solution was subjected to reduced pressure to distill off the acetone solvent to give a thick off-white solid, mp 100 to 110° C. GPC analysis of the starting materials and product shows adduct formation.

EXAMPLE 2

Rubber compositions containing the materials set out in Table I were prepared in a BR Banbury using two separate stages of addition. The sulfur and accelerators were added to the compounds during the second stage of mixing. The processing oils (naphthenic/paraffinic oil or the rosin modified succinamic acid) were added to the Banbury during the first stage of mixing. The processing oil was a mixture of naphthenic/paraffinic oils. The rosin modified succinamic acid was prepared in accordance with Example 1. Table II below sets out the physical data from the two samples.

Peel adhesion testing was done to determine the interfacial adhesion between the rubber formulations that were prepared. The peel adhesion was determined by pulling the compound away from itself at a right angle to the untorn test specimen with the two ends being pulled apart at a 180° angle to each other using an Instron machine. The area of contact was determined from placement of a Mylar sheet between the compounds during cure. A window in the Mylar allowed the two compounds to come into contact with each other during testing.

TABLE I Banbury Material Sample 1 Sample 2 Stage NAT 2200¹ 100 100 1 Processing oil² 5 0 1 Reaction product of Example 1 0 5 1 Carbon black (N299) 50 50 1 Antioxidant³ 2 2 1 Zinc Oxide 5 5 1 Sulfur 1.4 1.4 2 Accelerator⁴ 1 1 2 ¹Natsyn ® 2200, synthetic cis-1,4-polyisoprene from The Goodyear Tire & Rubber Company ²Flexon 641 from Exxon Mobil ³Quinoline type ⁴N-t-butyl-2 benzothiazole sulfenamide

TABLE II Control Sample 1 Sample 2 Stress-Strain 100%, (MPa) 2.06 2.16 150%, (MPa) 3.46 3.39 200% (MPa) 5.51 5.08 300% (MPa) 10.78 9.36 Brk Str. (MPa) 23.40 21.27 EL-Brk (%) 567 595 Energy, (J) 179.57 189.73 Hardness Room temperature 61.9 71.0 100° C. 56.6 61.4 Rebound, % Room temperature 46.7 42.5 100° C. 63.5 48.5 DIN Abrasion 136 172 Green Strength 40% .21 .35 80% .24 .44 120% .21 .44 240% .15 .37 480% .13 .31 Tensile @ break .10 .27 Elongation @ break 1477 752 Rheometer 150° C. Maximum torque 38.2 38.2 Minimum torque 7.5 8.1 Delta torque 30.7 30.1 T90 (min) 13.8 16.5 T25 (min) 10.0 10.8 T1 (min) 7.8 8 Reversion, 60 min 2.1 0.5

The results in Table II clearly show similar cure behavior, with the exception of improved reversion for Sample 2, and similar stress-strain properties for the Control (Sample 1) and Sample 2. However, Sample 2 exhibits higher hardness at room temperature and 100° C. and also lower rebound at the same temperature. This would be particularly advantageous for improved wet traction and wet or dry handling when applied to a tire tread compound, especially in higher performance type tires. The Sample 2 also exhibits improved green strength which would be beneficial for the “green compound” prior to the curing process for shaping during extrusion or calendering process.

While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention. 

What is claimed is:
 1. A composition comprising a rosin modified succinamic acid of the formula:

or mixtures thereof.
 2. The composition of claim 1 wherein the rosin modified succinamic acid is the reaction product of succinic anhydride and dehydroabietylamine.
 3. The composition of claim 1 wherein said composition is added to a rubber selected from the group consisting of natural rubber, homopolymers of conjugated diolefins and copolymers of conjugated diolefins and ethylenically unsaturated monomers.
 4. The composition of claim 3 wherein said composition is at a concentration of from about 1 part per hundred rubber to 50 parts per hundred rubber.
 5. The composition of claim 4 wherein said composition is at a concentration of from about 2 to 35 parts per hundred rubber.
 6. A process for preparing rubber compositions which comprises a mixing a rubber selected from the group consisting of natural rubber, homopolymers of conjugated diolefins copolymers of conjugated diolefins and ethylenically unsaturated monomers or mixtures thereof with the rosin modified succinamic acid of claim
 1. 7. The process for preparing rubber compositions according to claim 3 wherein the rosin modified succinamic acid is at a concentration of from about 1 part per hundred rubber to 50 parts per hundred rubber and is in an intimate mixture with said rubber.
 8. The process for preparing rubber compositions according to claim 4 wherein the rosin modified succinamic acid is at a concentration of from about 2 to 35 parts per hundred rubber.
 9. A rubber vulcanizate comprising the composition of claim
 3. 10. The rubber vulcanizate of claim 9 wherein said vulcanizate is selected from the group consisting of tires, motor mounts, rubber bushings, power transmission belts, conveyor belts, printing rolls, hoses, rubber shoe heels and soles, rubber floor tiles, caster wheels, elastomer seals and gaskets, wringers, hard battery cases, automobile floor mats, mud flaps for trucks and ball mill liner.
 11. The rubber vulcanizate of claim 10 wherein said vulcanizate is a tire. 